Hydroxylated alpha-olefin/non-conjugated diene polymer

ABSTRACT

AN HYDROXYLATED ALPHA-OLEFIN/NON-CONJUGATED DIENE POLYMER HAVING HYDROXYLATED SIDE CHAINS IN ADMIXTURE WITH CLAY, ZNO, ZNBF2, A PHENOL-FORMALDEHYDE RESIN OR POLYISOCYANATE. AN HYDROXYLATED ALPHA-OLEFIN-NON-CONJUGATED DIENE POLYMER HAVING HYDROXYL SUBSTITUTED SIDE CHAINS CONTAINING ONE HYDROXYL GROUP EACH AND OTHER SIDE CHAINS CONTAINING ETHYLENIC UNSATURATION AND A PROCESS FOR MAKING.

United States Patent Oflice 3,679,527 Patented July 25, 1972 3,679,627HYDROXYLATED ALPHA-OLEFIN/NON- CONJUGATED DIENE POLYMER Jerald R.Harrell, Anestis L. Logothefis, and John J. Verbanc, Wilmington, Del.,assignors to E. I. du Pont de Nemonrs and Company, Wilmington, Del.

No Drawing. Continuation-impart of application Ser. No. 764,328, Oct. 1,1968. This application July 9, 1969, Ser. No. 840,511

Int. Cl. C08d 11/00 U.S. Cl. 260-415 6 Claims ABSTRACT OF THE DISCLOSUREAn hydroxylated alpha-olefin/non-conjugated diene polymer havinghydroxylated side chains in admixture with clay, ZnO, ZnBr aphenol-formaldehyde resin or polyisocyanate. An hydroxylatedalpha-olefin/non-conjugated diene polymer having hydroxyl substitutedside chains containing one hydroxyl group each and other side chainscontaining ethylenic unsaturation and a process for making.

PRIORITY This application is a continuation-in-part of application Ser.No. 764,328, filed Oct. 1, 1968 and now abandoned.

BACKGROUND OF THE INVENTION It is well known to preparealpha-olefin/non-conjugated diene (ODM) polymers such as ethylene/dienedipolymers and ethylene/propylene/diene terpolymers and the like inwhich the diene is a non-conjugated diene with only one terminal doublebond (i.e., polymerizable double bond). Such polymers havesaturated-hydrocarbon-backbones which provide excellent resistance toaging, particularly in the presence of oxygen or ozone. However, becausethese polymers are relatively unreactive and generally have pooradhesive properties, they are useful only in a limited number ofapplications. There has been a need for polymers having the beneficialcharacteristics of these saturated-hydrocarbon-backbone polymers butwhich would also be capable of use in a wide variety of applications,particularly in cements, adhesives and latexes and in the preparation ofvulcanizates and derivatives.

SUMMARY OF THE INVENTION In accordance with this invention there isprovided an hydroxylated alpha-olefin/non-conjugated diene polymercontaining hydroxyl substituents in the amount of about 0.05-5 grammoles of hydroxyl groups per kilogram of polymer. The diene is anon-conjugated diene with only one polymerizable double bond (only oneof the double bonds polymerizes to any significant extent to form thebackbone of the polymers of this invention) and is preferably an acyclicnon-conjugated diene with only one terminal double bond. One species ofhydroxylated po1ymers can be prepared by heating the unmodified polymerwith diborane at about 25-250" C., treating the reaction product withoxygen and then an aqueous medium. Another can be made by reacting theprecursor polymer with performic acid. The modified polymer has someside chains with hydroxyl substituent groups and others with ethylenicunsaturation.

The hydroxylated polymers of this invention possess unique properties.Thus an admixture of the hydroxylated polymer with clay can be extrudedor molded and upon heating produces a vulcanizate which is rubbery andtough with good strength without conventional curing or the use ofcuring formulations normally required to produce vulcanized elastomers.

Similarly admixtures of the hydroxylated polymer with a heavy metaloxide or halide such as zinc oxide or zinc bromide upon heating producea cured stock free from bloom and sulfur odor and having excellent colorretention compared with sulfur cured systems. Mixtures of anhydroxylated polymer latex with conventional resorcinolformaldehyderesins used in automobile tire cord dips are useful as tire cord dipswhile compositions of the hydroxylated polymers containingpolyisocyanates are suitable for bonding alpha-olefin/diene rubbers topractically any substrate. The latter compositions can also be used as abonding agent in conventional paper-making machinery to preparepaper-like non-woven sheets from synthetic fibers.

DETAILS OF THE INVENTION where the wavy line represents the polymerbackbone. When hydroxylated by other procedures, as by treatment withperformic acid, each hydroxylated side chain can contain two hydroxylgroups on adjacent carbon atoms, and other side chains can contain othersubstituents such as epoxide or formate ester groups.

The alpha-olefin used in preparing the ODM precursor polymer can beethylene or a higher alpha-olefin. Preferred precursor polymers areterpolymers having the composition ethylenelC c alpha-olefin/aliphaticdiene, the alpha-olefin being propylene, l-butene, Z-butene, 1- pentene,etc.

The dienes useful in preparing the ODM polymers useful in this inventionare non-conjugated dienes containing only one polymerizable double bond.Preferred are C -C aliphatic dienes with only one terminal double bondsuch as 1,4-hexadiene, 1,4-heptadiene, 1,5-heptadiene, 1,5-octadiene andthe like. Useful cyclic dienes include dicyclopentadiene;1,5-cyclooctadiene, 5-alkenyl-2-nor bornenes such as5(1-butenyl)-2-norbornene; 5-alkylidene-Z-norbornenes such asS-ethylidene-Z-norbornene and 5-methylene-2-norbornene. Other dienes ofthis type are well known in the art and can be utilized in thisinvention so long as they provide or can be modified to provide the ODMprecursor polymer with pendant groups containing hydroxyl substituentsand side chain ethylenic unsaturation such as disclosed herein.

The diene monomeric unit in the polymer can be present in the amount ofabout 3% to as much as 25-30% by weight of polymer in the case of cyclicdienes. Aliphatic diene monomeric units are present in the amount ofabout 3 to 12% by weight of polymer and preferably in the amount of 3-7%on this basis.

The precursors polymers are known to the art, and the art is also wellaware of how these polymers can be made. Representative polymers aredisclosed in US.

3 2,933,480, US. 3,093,620 and U.S. 3,093,621. Thehydroxylated polymersof this inventionmay be prepared by reacting a conventional ODM polymerin solution in an inert solvent with diborane (B H at about roomtemperature to 250 C., preferably at an elevated temperature of about 50C. to 225 C. In place of diborane there can be utilized amine boranessuch as trialkyl amine boranes (R N-BH THF-BH etc. where R is C -Calkyl, such as methyl, ethyl, propyl or butyl. Amine boranes which arestable oils or solids at room temperature should be used at highertemperatures such as 80 C. or

b above at which temperatures the position of the equilibis shiftedsubstantially to the right. A preferred trialkylamine borane istrioctylamine borane. Following completion of the reaction the productis oxidized and then hydrolyzed to produce an hydroxylated polymer ofthis invention with each hydroxylated side chain containing one hydroxylgroup. The polymer also contains ethylenic vunsaturation in side chainsformed by the diene monomer unit which are not hydroxylated. Thepolymers can contain about 0.05-5 gram moles hydroxyl per kilogram ofpolymer but preferably about 0.11 gram mole on this basis. The hydroxylsare not attached to the backbone of the polymer but rather to pendantcarbon chains and similarly the ethylenic unsaturation is in pendantcarbon chains.

The oxidation of the polymer-diborane reaction product can be effectedby air, molecular oxygen, hydrogen peroxide or other suitable oxidizingcompounds. Three atoms of oxygen are provided for each atom of boron.Oxidation is effected simply by exposure to air at room temperature forat least a few minutes. Hydrolysis occurs almost automatically due tomoisture present in the polymer solution but additional water can beadded if needed. Following oxidation and hydrolysis, the polymer can beisolated from the solvent using conventional procedures such as steamdistillation or precipitation. Alternatively the crude reaction productcomprising the hydroxylated polymer in the organic solvent can be useddirectly as a cement or adhesive. Also, the solvent solution of polymercan be admixed with an aqueous medium containing a dispersing agent toform a latex useful for impregnation of fabrics or as a coatingcomposition or adhesive.

' Alternatively the precursor polymer can be hydroxylated by reactionwith performic acid in an organic solvent at a temperature above roomtemperature (preferably at about 30-50 C.) for a period of 1 to 3 hours.It is thought that performic acid reacts with the carbon atoms joined bythe ethylenic double bonds in the side chains to produce hydroxylatedpendant groups. The-polymer .product can be recovered in anyconventional manner as described above or the reaction product solutioncan be utilized directly as a cement or converted to a latex.

Polymers of this invention which contain two hydroxyl groups perhydroxylated side chain are used in the same -manner as the polymerswith monohydroxyl pendant groups, and for the-same purposes. The extrahydroxyl group does not appear to adversely alfect the polymerperformance.

The hydroxylated polymers of this invention which are prepared byreacting an alpha-olefin/non-conjugated diene polymer with 'performicacid normally contain epoxy groups and formoxy (formate ester) groups aswell as hydroxy groups attached to hydrocarbon side chains, and 'in someinstances the latter can be present in less than a major proportion,although the usefulness of the poly- ;(ML. 1+4/121 C.) and containing36% propylene units, 58.3% ethylene units and 5.7% 1,4-hexadiene unitsand with side chains containing ethylenic unsaturation (0.46 mol/kg.)upon heating for three hours at 35 C. as a 4.5% solution intetrachloroethylene in the presence of 555 g. of formic acid and 104 ml.of 30% hydrogen peroxide, produces a product which analyzes for thefollowing functionality (moles per kilogram of polymer); (C -C), 0.19;epoxy, 0.17; formate ester, 0.1; hydroxyl, 0.10 or more (e.g., OHadjacent to formate ester or as glycol). When this product is heated fornine hours at C. with paratoluene sulfonic acid it is converted to apolymer which analyzes for the following functionality (moles/kg. ofpolymer); C=C, 0.20; epoxy, zero; formate ester, 0.26; hydroxyl, 0.26 ormore (as OH adjacent to formate ester or glycol). When this product isin turn heated for 16 hours at 85-90 C. in tetrachloroethylene (2%weight/volume solution) in the presence of 280 parts of 10 molar ofsodium hydroxide and 6 parts (based on the polymer) of an 85% solutionof a quaternary ammonium chloride in a 50/50 mixture of water andisopropanol, the chloride having the formula 1 e R-N-RCl where R is amixture of C -C alkyl (predominantly Cm-Cn) and R, is

the product analyzes as free from epoxy and formate ester groups andshows only O=C groups (0.20 mole/ kg.) and hydroxyl groups (0.52)(present in glycol) attached to side chains.

On the other hand when g. of this ethylene/propylene/1,4-hexadienepolymer is allowed to stand atroom temperature for 16 hours as a 4.5%(weight/weight) solution in tetrachloroethylene with 88 g. of 40%peracetic acid in acetic acid there is produced a polymer having a smallamount of hydroxyl groups attached to the side chains and containing noester groups but a preponderance of epoxy groups (0.44 mole per kg.).All of these products analyze for significant ethylenic unsaturation inside chains of the polymer which permits vulcanization with sulfur. Allof the aforesaid polymers contain hydroxy groups attached to some of thepolymer side chains and ethylenic unsaturation in others and are usefulin the several embodiments of this invention.

Solvents useful for preparing the precursor alpha-olefin/diene polymersare generally suitable for carrying out the hydroxylation process ofthis invention. Representative solvents include tetrachloroethylene,n-hexane, n-pentane, n-heptane and the like. The art is well aware ofsuit-.

able solvents for this purpose.

Hydroxylated polymers of this invention have a wide variety ofutilities. They provide excellent direct adhesion to many materialsincluding cotton, rayon and wool. Mixtures of these hydroxylatedpolymers with polyisocyanates provide superior adhesion to glass, metals(e.g., aluminum), wood, natural or synthetic polymers such aspolyamides, acrylics and polyesters, whether in the form of films orfibers, and provide excellent laminates of these materials havingexceptionally strong peel strength as shown in the examples below. Forsuch use as adhesives in preparing laminates or as coating compositions,the hydroxylated polymers are usually in the form of solutions orlatexes.

Hydroxylated polymers of this invention can also be mixed with pigments,fillers or other additives (e.g., clays, carbon black, antioxidants,stabilizers, light filters and the like) conventionally used in therubber art to extend or 7 color elastomeric polymers. In one specificembodiment of this invention an hydroxylated polymer is admixed withabout phr. (parts per hundred parts polymer by weight) of a hard kaolinclay and molded at 100 C.

under pressure to produce an elastomeric composition which is rubbery,tough and has good strength without conventional curing. Thisclay-extended product can also be extruded and provides an elastomericcomposition having the properties of a cured polymer but without theseparate curing step or the curing formulations normally required. Theamount of clay can vary from about thirty to several hundred parts perhundred parts polymer by weight (phr.). Other clays are useful but hardkaolin is preferred as producing the best product properties.

According to another embodiment of this invention hydroxylated polymeris reacted with an excess polyfunctional isocyanate which is preferablya diisocyanate but can be a trior higher functional isocyanate. Theisocyanate can be aliphatic or aromatic as desired depending upon theultimate properties which are needed. Reaction of the hydroxylatedpolymer with the isocyanate provides an adhesive with an exceptionalbonding strength. Fillers such as clay, carbon black and the like canalso be incorporated without adversely affecting the strength. Similarlythe hydroxylated polymer can be reacted with 6-18 phr., preferably 12.phr. of phenolic resin such as phenolformaldehyde resin to producecompositions with great cohesiveness and resistance to heat and abrasionmaking them useful as automobile brake linings. The hydroxylatedpolymers in all of these compositions can also be cured by conventionalmeans as, for example, with sulfur or peroxides to add additionalstrength to the ultimate composition.

According to still another embodiment of this invention, an hydroxylatedpolymer is reacted with 3-10 phr. of a heavy metal oxide (e.g., ZnO) or0.54 phr. of a heavy metal hydroxide or halide (e.g., zinc hydroxide,zinc bromide) in the presence of a long-chain fatty acid (e.g., stearicacid) to produce a cured stock free from bloom and sulfur odor andhaving excellent color retention compared to sulfur cured system. Otheroxides and halides which can be utilized includethose of aluminum, lead,magnesium, cadmium, iron, etc., alone or in combination. These curedcompositions appear to exhibit the best properties of correspondingsulfur-cured polymers of the same type but without the deficiencies ofsuch products.

The following examples illustrate the invention. All parts, percentagesand proportions are by weight unless otherwise indicated. The followingcopolymers are used in the examples. Tensile test data refers to samplestrips 0.635 x 0.19 x 12.7 cm. in size.

POLYMER A Polymer A is made by copolymerizing ethylene with propyleneand 1,4-hexadiene in solution in tetrachloroethylene in the presence ofa coordination catalyst formed in situ by mixing vanadium oxytrichloridewith diisobutyl aluminum monochloride in accordance with the generalprocedure of U.S. Pat. 2,933,480. Polymer A has a Mooney viscosity(ML-4/ 121 C.) of about 70 and contains about 40 weight percentpropylene units, 6.6 weight percent total 1,4-hexadiene units and 53.4weight percent ethylene units. The sulfur-curable unsaturation amountsto about 0.61 g.-mol (B C/kg. by infra-red analysis.

POLYMER B Polymer B is made substantially the same way as Polymer Aexcept that the proportion of 1,4-hexadiene is lower. Polymer B has aMooney viscosity of about 70 and contains about 44 weight percentpropylene units, 3.5 weight percent total 1,4-hexadiene units and 52.5weight percent ethylene units. The sulfur-curable unsaturation amountsto about 0.22 g.-mo1. (:C/kg. by infra-red analysis.

POLYMER C Polymer C is made by the same general procedure as Polymer Aexcept that hydrogen modification is employed during the polymerizationto lower the Mooney viscostiy of the copolymer to about 40. Polymers Aand C are 6 alike in their monomer composition and their degree ofunsaturation.

POLYMER D Polymer D is made by the same general procedure as Polymer Bexcept that hydrogen modification is employed during the polymerizationto lower the Mooney viscosity to about 40. Polymers B and D are alike intheir monomer composition and their degree of unsaturation.

EXAMPLE 1 Hydroxylation of Polymer A 30.3 liters (50.9 kg.) of a 4.6weight percent tetrachloroethylene solution of Polymer A (2330 grams),15.15 liters of tetrachloroethylene and 16.9 liters of 98% formic acidare charged to a 75.7 liter Pfaudler kettle at 25 C. Then 7860 ml. of30% aqueous hydrogen peroxide is added dropwise over a 75-minute period,cooling being applied when necessary to keep the temperature below 35 C.Stirring with intermittent cooling is continued for minutes. Then 5grams of 4,4'-thio-bis(3-methyl)-6- tert-butylphenol antioxidant isadded. After five minutes, stirring is stopped and the reaction mixtureallowed to separate for 30-45 minutes. The tetrachloroethylene lowerphase, containing hydroxylated Polymer A, is drawn off and the formicacid present is partially neutralized with ammonium hydroxide. Thepolymer solution is then pumped to a modified centrifugal pump,thoroughly mixed with water and introduced into a glass settling towerwhere the separating organic layer is automatically fed to the nextwashing pump. After leaving the third washing and settling stage, theorganic layer, free now from reactants and salts, is dropepd into acollection vessel. The hydroxylated Polymer A, isolated by drum dryingweighs 2040 grams. Its inherent viscosity, measured on a 0.1% solutionin tetrachloroethylene at 30 C., is 2.95, its Mooney viscosity is 67,and its unsaturation amounts to 0.22 g.-mol of C=C/kg. measured byinfra-red analysis. The polymer exhibits an hydroxyl content of about0.12 mol/ kg. of polymer.

Hydroxylation of Polymer C Analysis:

O=0.35 mole/kg. Epoxy-0.19 mole/kg, *Formate ester0.10 mole/ kg.HydroxylzFormate EsterzO. 10

Polymer C is hydroxylated by the same procedure used Polymer A. Theproduct has about 0.3 g.-mole/kg. of sulfur-curable ethylenicunsaturation by LR. analysis and about 0.1 g.-mole/ kg. of hydroxylgroups.

EXAMPLE 2 Curing of hydroxylated Polymer A with a diisocyanate is curedin a pre-heated press at 160 C. for one hour. The resulting vulcanizatehas the following properties at 25 C.:

Stress-strain properties Stress at 100% extension (kg./cm. )28.1 Stressat 200% extension (kg./cm. )73.1 Stress at 300% extension (kg./cm.)--'133.6 Tensile strength at break (kg./cm. )--142.0 Extension at break(percent)310 Tensile set (percent)-11 7 EXAMPLE 3 Curing of hydroxylatedblack stocks with ZnO and ZnBr Each of Polymer B and hydroxylatedPolymer A are compounded on a room temperature rubber roll mill asfollows:

Parts by weight Polymer 100. SAF carbon black 50. Stearic acid 0.5 or 1.

Tester at 50.8 cm./min. at 25 C. are given in Table I g which shows thathydroxylated Polymer A containing only carbon black and stearic acid canbe cured using ZnO and/or ZnBr; as sole curing agents. Polymer -B blackstock does not cure with Zn-O or ZnBr Very good tensile properties areshown by the hydroxylated Polymer A black stock (G) when ZnO and ZnBr;are used in combination.

8 EXAMPLE 5 Curing black loaded hydroxylated Polymer A with oil solublephenolic resin Hydroxylated Polymer A is compounded on a rubber rollmill at room temperature with SAP carbon black, zinc oxide, stearic acidand phenolic resin.

For purposes of comparison a similar stock containing no phenolic resinis prepared and analogous compositions are made wherein Polymer B issubstituted for hydroxylated Polymer A. All stocks are then pressed intoslabs and heated at 160 C. for one hour. Table III gives theformulations and the vulcanizate properties of the stocks at C. Theaddition of the phenolic resin enhances the tensile properties of theblack loaded hydroxylated polymer stock. Controls based onnon-hydroxylated polymer do not cure. The phenolic resin, commerciallyavailable from Schenectady Chemical Company as Resin SP 1055 has aspecific gravity of 1.00-1.10, a melting point in the range 125-145 F.,a bromine content of -39% by weight and a methylol content in the rangeof 10.00- 12.5% by weight. This oil soluble material is prepared byreacting an excess of formaldehyde with 1,1,3,3-tetramethylbutylphenol.

TABLE I A B C 1 D E 3 F l G H Hydroxylated Polymer A 100 100 100 100 100100 Polymer B- 100 100 SAF Carbon Black 50 50 50 50 50 50 50 Stearieacid 0. 5 1 1 0. 5 O. 5 1 1 1 ZnBrz- 2 2 1 2110 5 5 5 5 5 Stress at:

extension (kg/em!) 9. 1 17. 6 7. 4 14. 1 l7. 6 7. 7 30. 2 17. 6 200%extension (kg/0111. 11. 2 45. 7 6. 7 24. 6 38. 6 6. 3 86. 5 32. 3 300%extension (kgJcmJ). 14. 8 121. 6 6. 3 47. 1 85. 8 6. 6 182. 8 61. 9Tensile strength (kg./cm. 16. 2 154. 7 6. 0 116. 0 179. 3 5. 3 229. 2129. 4 Elongation at break (percent)- 350 340 660 480 430 430 350 500Tensile Set (percent)- 35 9 127 6 13 86 6 23 l Polymer B outside thisinvention. 1 Stock placed on 0. mill for 3 minutes after compounding.

EXAMPIJE 4 45 TABLE III Curing of hydroxylated Polymer A black stocks AB C l D I with sulfur mo Hydroxylated Polymer A is compounded accordingto igg T 0 the automobile tire carcass stock formulation given 5 5 5below: 1 1 1 Phenolic resin 12 12 Parts i tio y t 1 (k I e 21 A e ex enson g. cm. 17. 1 7. 7 10. 5 HYdmxylatPd Polymer A 100 2007; extension(kg./cm. 32. a s1. 9 a 3 11, 2 Hlgh abrasion furnace black 80 T agmt g igfi 7 3 2 1%, 2 5 g g v ens e a rea g. cm. 0. 1 5. 5 Naphflmmc petroleum011 47 s Elongation at break (percent) 500 400 430 980 ZnO 5 Tensile set(percent)-.- 23 10. 86 115 W I l Polymer B (not hydroxylated) havingsame C=C content as by- Zinc benzothia zylsulfide droxylated Polymer Ais outside invention. Zisc dibenzyldithiocarbamate 2.5

Test slabs are cured at C. for 30 minutes. For comparison a similarcarcass stock containing |Polymer B in place of hydroxylated Polymer Ais also cured. The vulcanizate properties at 25 C. are shown in TableII.

EXAMPLE 6 Mineral filled hydroxylated Polymer A stocks HydroxylatedPolymer A- is compounded with a mineral filler to yield an elastomericcomposition which is tough and has good strength without curatives beingadded.

Hard kaolin clay is an air-floated clay containing 44-46% silica,37.539.5% alumina, 1.5-2% iron oxide and 1-2% titanium dioxide byweight, the ignition loss being 13.9-14.2% by weight. The moisturecontent (maximum) is 1% by weight. The pH (in water) is about 4.5-5.5.This clay has a specific gravity of 2.60; a 325-mesh screen residue of0.17% by weight and the following particle size distribution (byweight): above 10,1, 0.1%, 5-10 2.8%; 4-5 1.5%; 3-4p, 2.3%; 2-3 1, 3.4%;1-2n, 9.0%; 0.5-1n, 19.0%; 0-0.5. 61.9%.

TABLE IV Hydroxylated Polymer A Polymer B Stress at 100% elongation(kg./cm. 45. 7. 73 Tensile strength (kg/cm!) 59. 1 4. 9 Elongation atBreak (percent) 170 300 Tensile set (percent) 11 107 1 Outside thisinvention. Polymer B has substantially the same Mooney viscosity andunsaturation as hydroxylated Polymer A.

Other samples of the clay stocks above were compounded on a rubber millusing the following sulfur formulation:

Parts by weight Elastomer+hard kaolin (120 phr.) 220 Naphthenicpetroleum oil 20 ZnO Stearic acid 1 Sulfur 2.5 Tetramethyl thiuramdisulfide 3 Z-mercaptobenzothiazole 1 After these formulations are curedfor 30 minutes at 160 C., the tensile properties shown in Table V areobtained on 0.63 cm. strips using an Instron Tensile Tester.

The hydroxylated Polymer A stock has much improved tensile and modulusproperties. A further enhancement of tensile properties is obtained byheating the hydroxylated Polymer A stock on a hot mill as shown in theabove table.

ADHESION Adhesive cement preparation A 5.5-g. portion of ISAF-lOF carbonblack containing naphthenic petroleum oil is added to 150 ml. of1,1,1-trichloroethane in a Waring Blendor; the blender is run at highspeed until the black has been dispersed (as shown by brushing a stripof the dispersion on aluminum foil). Approximately 50 m1. of1,1,1-trichloroethane are used to wash down the sides of the blenderduring this operation. Finally, a solution of 10 grams of hydroxylatedpolymer in 300 ml. of 1,1,1-trichloroethane is added while the blenderis operated at high speed. When a diisocyanate is also present, it isintroduced just before the cement is applied to the substrate.

PREPARATION OF TEST PIECES (1) Peel test slabs A 7.6 x 15.2 cm. piece ofa textile fabric is given five coats of a cement being tested. After thecoated fabric is dried at 80 C. for one hour at 360 mm. in a nitrogenstream, it is placed in a 7.62 x 15.2 x 0.069 cm. mold with the coatedside up. A 20-25 g. slab of Polymer B carcass stock formulation given inTable VI is placed against the coating on the fabric in the mold; cottonduck backing is 10 adhered to the other side (upper) of the carcassstock. This assembly is cured in a press for 35 minutes at 160 C. (moldsloaded and unloaded hot). Strips 1.27 cm. wide are then stamped out andpulled apart on an Instron Tensile Tester at a speed of 5.08 cm./min. AT-peel or peel is used.

TABLE VI Parts Polymer B High abrasion furnace black 80 Naphthenicpetroleum oil 47.5 ZnO 5 Stearic acid 1 Sulfur 1.5 Zincbenzothiazylsulfide 1.2 Zinc dibenzyldithiocarbamate 2.5

(2) H-pull specimens The cement is brushed onto the tire cord and thecoated cord is dried at 80 C. for one hour at 360 mm. Hg in a nitrogenstream. The pick-up is about 1% by weight.

The coated cord is then used to conduct single-cord adhesion tests orH-pull tests as described in India =Rubber World, 114, pp. 213-217(1946). The mold has channels 0.63 cm. deep and 0.63 cm. wide connectedby slots 0.95 cm. long. The coated cord samples are molded as describedin the above reference into Polymer B carcass stock and the assemblies,initially at 25 C., heated for 45 minutes at C. under pressure. Theresulting composite articles are tested as describedin the reference(head speed 5.08 cm./min.).

Bonding Polymer B carcass stock to rayon with hydroxylated Polymer CSome 7.62 x 15 .2 cm. swatches of mono filament rayon fabric having aflat 2 x l weave with a count of 84 (warp) x 38 (fill) are scoured toremove conventional textile finishes by immersing in an aqueous solutionof 0.1% sodium salt of modified alcohol sulfate and 0.1% Na P0 at 80 C.for 30 minutes. Finally they are water rinsed and air dried.

Half of each swatch is coated five times on one side with a cement madefrom a polymer (see Table VII) 1,1,1-trichloroethane, and ISAIF carbonblack (with petroleum oil) prepared by the general procedure givenabove. Each coat is air dried for about one minute before applymg thenext. The coated fabrics are hung for one hour in an 80 C. oven atone-half atmospheric pressure and swept by a stream of nitrogen.

A 7.62 x 15.2 cm. mold is preheated to 160 C. and loaded, in turn, withone of the above coated rayon swatches (coated side up), 20-25 g. ofPolymer 13 Carcass Stock and covered with an untreated canvas duckfabric. The assembly is then pressed at about 131.8 kg./cm. (13,600 kg.on a 10.2-cm. ram in a Pasadena Press) for 35 minutes at 160 C.Exclusive of the rayon, the cured assembly is about 0.20 cm. thick.

The fabric adhesion data for the resulting adhered assembly are given inTable VII. 1

TABLE VII T-peel values (kg/cm.)

Polymer B carcass stock adhered to rayon fabric Polymer in cement:T-peel at 25 C. Hydroxylated Polymer C 5-6.1

the cement containing hydroxylated Polymer A is replaced by hard kaolinclay, the peel value is about 4.6; if clay wholly replaces the black,the peel value is about 3.9.

EXAMPLE 8 Bonding Polymer B carcass (black) stocks to nylon fabric,polyester fabric and glass fabric with hydroxylated Polymer C The nylonfabric used is 7.6 x 15 cm. piece of monofilament fabric having a plainweave and a count of 60 (warp) x 40 (fill). Before being used, the nylonfabric and a similarly constructed polyethylene terephthalate fabricateimmersed in an aqueous solution of 0.17% sodium salt of modified alcoholsulfate and 0.1% Na PO at 80 C. for 30 minutes, water washed and airdried. The glass-used is continuous filament spun tape; .018 cm. thick,yarn size 150%; thread count 42 x 22.

Cements are made from hydroxylated Polymer C as described in Example 7and some cements also contained methylene bis(4-phenyl isocyanate). Thefabrics are coated TABLE vm [T-Peel values (kg./cm.) Polymer B carcassstock adhered to fabric by hydroxylated Polymer C cements] Diisocyanatel disocyanate Fabric present absent N ylon. 5-8. 9 1. 3-1. 4 Polyester3. 2-3. 7 0. 5-0. 6

las 5-5.

l Methylene bis(4-phenylisocyanate). I Not determined.

When Polymer B is substituted for hydroxylated Polymer C, in thediisocyanate-containing cement, the following data are obtained:

TABLE IX Fabric: T-peel (kg/cm.) Nylon 0.5 Polyester 0.4 Glass 1.2

EXAMPLE 9 Bonding Polymer B carcass (black) stocks to nylon fabric andpolyester fabric with hydroxylated Polymer A The nylon and polyesterfabrics described above are coated with cements based on hydroxylatedPolymer A (containing -methylene bis(4-phenylisocyanate)) and bonded toPolymer B carcass stock by the same procedure as described for thecorresponding hydroxylated Polymer C in Example 8. Cements are also madewherein the ISAF-IOF carbon black is replaced by a 5.0 g. of clay or amixture of 2.75 g. ISAF-IOF black/ 2.5 g. clay. T-peel adhesion data(measured at 25 C.) are given in Table X.

TABLE X [T-p'eel values (kg./cm.) Polymer 13 carcass stock adhered tofabric by hydroxylated Polymer A cements ISAF ISAF/clay Clay presentpresent present Fabric in cement in cement in cement Nylon 2. 8-3. 1 a.7 2. 9-3 Polyester--. 1. 8-3. 3 1. 5 1. 3-1. 5

1 0.0075 g./ml. of methylene bis (4-phenylisocyanate) in the cement.

is omitted with the following results:

12 EXAMPLE 1o Bonding Polymer B carcass (black) stock to nylon tire cordwith hydroxylated Polymer C cement Adhesion to coated cord, kg. H-pullat 25 C. 7.9 H-pull at C. 4.5

For purposes of comparison, Polmer B is substituted for hydroxylatedPolymer C in the cement with the following results:

Adhesion to coated cord, kg. H-pull at 25 C. 3.5 H-pull at 100 C 2.4

EXAMPLE l1 Bonding Polymer B carcass (black) stock to polyester andaluminum film with hydroxylated Polymer C Polyethylene terephthalatefilm and aluminum film are each given three coats of the above-describedcement containing hydroxylated Polymer C, ISAF-lO carbon black,1,1,1-trichloroethane and methylene bis(4- phenylisocyanate) (0.0075g./ml. of cement). The coated films are pressed against the PolymerB-based carcass (black) stocks in a preheated 7.62 cm. x 15.2 cm. moldunder pressure at C. for 35 minutes. T-peel values for the resultingcomposite articles are measured at 25 C. For purposes of comparison inpolyester adhesion, the diisocyanate content is lowered to 0.0015g./-ml. in one cement and increased to 0.015 g./ml. in another. Forpurposes of comparison in the aluminum adhesion, the diisocyanate TABLEXI [T-peel (kg/cm.) for cements] Diisocyanate 0. 0 0. 0015 0. 0076 0.015 Film g./m1. g./m.l. g./ gJml.

Polyester 2. 5, 8. 4 8. 9, 8. 9 7. 9, l2. 5 Aluminum 1. 3, l. 3 7. 5,6.8

1 Not determined.

When Polymer B is substituted for hydroxylated Polymer C in the cementcontaining 0.0075 g./ml. methylene bis(4-phenylisocyanate), the T-peelvalues for adhesion to polyester film at 25 C. are only 0.2 and 0.4kg./cm.

When Polymer C is substituted for hydroxylated Polymery C in the cementcontaining 0.0075 g./ ml. methylene bis(4-phenylisocyanate) the T-peelvalue for adhesion to aluminum are very low-about 0.07.kg./cm.

EXAMPLE 12 Polymer E 13 of EPS Polymer E. The product has an inherentviscosity of 0.8 and contains 51.7% ethylene, 45% propylene and 3.3%1,4-hexadiene by weight. The sulfur curable unsaturation is about 0.3mol C=C/ kg.

Preparation of hydroxylated Polymer E A solution of 100 grams of PolymerE in one liter of heptane is treated with 15 ml. of diisoamyl borane.The temperature rises to 50 C. When infrared spectra of aliquote removedfrom the reactor no longer exhibit a (:C band at 10.37 microns, thereaction mixture is treated, while well stirred and cooled, with 100 ml.of 3 N NaOH, followed by 100 ml. of 30% aqueous hydrogen peroxide. Whenrefluxing subsides, the mixture is heated for a total reflux time of twohours. The mixture is cooled and the resulting emulsion is broken byacidification with sulfuric acid. The organic layer is concentrated byevaporation of the solvent and the residual hydroxylated Polymer E iswashed four times with methanol. The weight, after vacuum oven drying ofthe sample, is 90 grams. Hydroxylated Polymer E analyzes 0.74 g-molsOH/kg.

When hydroxylated Polymer E is substituted for the hydroxylated polymersutilized in Examples 2l1, substantially equivalent results are obtainedshowing that polymers having single hydroxyl groups attached to the sidechains, such as hydroxylated Polymer E, are as effective for purposes ofthe present invention as the polymers, such as hydroxylated Polymer A,which can have two hydroxyl groups attached to the side chains.

EXAMPLE 13 An EPDM polymer is made by copolymerizing ethylene, propyleneand 1,4-hexadiene in tetrachloroethylene at 28.1 kg./cm. in the presenceof a coordination catalyst formed in situ by combining VCL; anddiisobutyl aluminum monochloride. The EPDM product contains 70% ethyleneunits, 18.9% propylene units and 11.1% total 1,4-hexadiene units byweight. The unsaturation (by bromine absorption corrected forsubstitution) is 1.0 O=C gram-mole/kg. polymer. The Wallace Plasticityis 45 (corresponding to ML-4/ 121 C. Mooney Viscosity of 67).

After 1590 ml. of 98% formic acid has been added to a 4.5% solution of125 g. of the EPDM polymer in tetrachloroethylene at 30 C., 500 ml. of30% aqueous hydrogen peroxide is added with stirring over a 1.5-hourperiod while the temperature is maintained at 30-35 C. Stirring iscontinued for one more hour. The reaction product mixture is washed withwater containing a small amount of sodium hydroxide and isopropanol,washed with water several times and drum dried. The hydroxylated EPDMpolymer thus prepared contains about 0.87 gram-mole hydroxyl/kg. and0.13 gram-mole C=C/kg. by bromine analysis.

Solution A is prepared by mixing 90 grams of hydroxylated EPDM, 1800 ml.of hexane and 210 ml. of isopropanol. An emulsion is made by adding halfof Solution A to a homomixer containing a soap solution prepared from450 ml. water and 36 ml. of aqueous anionic surfactant (an alkyl arylsulfonate sold commercially as Naccanol 90F). After the emulsion hasbeen agitated for an additional four minutes at room temperature, hexaneand isopropanol are stripped oif at 75 C. at atmospheric pressure andthen under vacuum at 100 C. The resulting latex is creamed with 4 phr.sodium alginate (based on 100 parts of hydroxylated EPDM). The upperlayer is a concentrated latex having 50-52 weight percent solids; theparticle size is less than two microns.

A RFL composition is made by aging the folowing mixture for 6 hours atroom temperature; 61 g. water; 2.8 g. resorcinal; 3.8 ml. 37% aqueousformaldehyde;

. and 1.0 ml. of 8% aqueous sodium hydroxide.

A tire cord dip is made by aging the following mixture for about 17hours at room temperature: 8 g. latex of hydroxylated EPDM; 5.8 ml.water; 0.47 ml. 28 wt. percent aqueous ammonium hydroxide; and 11 ml. ofthe above RFL composition.

7.5 x 15 cm. square woven nylon swatches are coated with thehydroxylated EPDM tire cord dip and dried for 30 minutes at 100 C. Thepick up (dry basis) is about 10-15 weight percent.

The coated nylon is adhered to a 3.8 mm. slab of carcas. stock (seebelow) by heating in a plunger mold at 160 C. for 30 minutes. The peeladhesion is typically 5.9 kg./cm.

Carcass composition:

Parts by weight Polymer B said diene containing only one polymerizabledouble bond, vulcanizable polymer containing about 0.05-5 gram moleshydroxyl groups per kilogram of polymer, the hydroxyl groups beingattached to hydrocarbon sidechains, in admixture with at least oneadditive of the group; heavy metal oxide in an amount of about 3-10parts per 100 parts of polymer, heavy metal halide in an amount of about0.5-4 parts per 100 parts of polymer, and clay in an amount of about 30to about several hundred parts per 100 parts of polymer, with theproviso that when the additive is heavy metal oxide or heavy metalhalide a long-chain fatty acid is present.

2. The composition of claim 1 in which the hydroxylated polymer is anhydroxylated ethylene/propylene/ nonconjugated diene polymer.

3. The composition of claim 2 in which the additive is a hard kaolinclay.

4. A cured composition of claim 3.

5. The composition of claim 2 in which the additive is zinc oxide orzinc bromide.

6. A cured composition of claim 5.

References Cited UNITED STATES PATENTS 3,525,720 8/1970 Wismer et al.3,042,661 7/ 1962 Kirschenbaum et al. 26094.7 3,082,192 3/ 1963Kirschenbaum et al.

260-8078 3,301,908 1/1967 Dereich 26041.5 A 3,382,215 5/ 1968 Baum.

3,448,174 6/1969 Loveless et al. 260878 3,462,516 8/1969 Smith et al.26045.5 A

FOREIGN PATENTS 1,110,095 4/ 1968 Great Britain.

OTHER REFERENCES Du Pont-Development Products Report #18, ECD- 330,(December 1961), pp. 3 and 6.

ALLAN LIEBERMAN, Primary Examiner H. H. FLETCHER, Assistant ExaminerU.S. Cl. X.R.

16ll76; 260-293, 41.5 A, 77.5 AT, 80.75, 80.78, 94.7 A

